Sebastian Broch

Missing gas-phase source of hono inferred from zeppelin measurements in the troposphere

On a Zeppelin Nitrous acid (HONO) is an important atmospheric trace gas that acts as a precursor of tropospheric hydroxyl-radicals (OH), which is responsible for the self-cleansing capacity of the atmosphere and which also controls the concentrations of greenhouse gases, such as methane and ozone. How HONO is made is a mystery. Flying onboard a Zeppelin over the Po Valley in Northern Italy, Li et al. (p. 292) discovered HONO in the undisturbed morning troposphere, indicating that HONO must be produced there, rather than mixed from the surface. The high HONO concentrations are likely to have been formed by a light-dependent gas-phase source that probably consumed OH or HO2 radicals, which hints that the impact of HONO on the abundance of OH in the entire troposphere may be substantially overestimated. The tropospheric production of HONO from a light-dependent gas-phase source raises questions about its impact on OH. Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth’s surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.

Response to Comment on “Missing gas-phase source of HONO inferred from Zeppelin measurements in the troposphere”

Ye et al. have determined a maximum nitrous acid (HONO) yield of 3% for the reaction HO2·H2O + NO2, which is much lower than the yield used in our work. This finding, however, does not affect our main result that HONO in the investigated Po Valley region is mainly from a gas-phase source that consumes nitrogen oxides.

Wintertime photochemistry in Beijing: observations of RO x radical concentrations in the North China Plain during the BEST-ONE campaign

The first wintertime in situ measurements of hydroxyl (OH), hydroperoxy (HO2) and organic peroxy (RO2) radicals (ROx= OH+HO2+RO2) in combination with observations of total reactivity of OH radicals, kOH in Beijing are presented. The field campaign “Beijing winter finE particle STudy – Oxidation, Nucleation and light Extinctions” (BEST-ONE) was conducted at the suburban site Huairou near Beijing from January to March 2016. It aimed to understand oxidative capacity during wintertime and to elucidate the secondary pollutants’ formation mechanism in the North China Plain (NCP). OH radical concentrations at noontime ranged from 2.4× 106 cm−3 in severely polluted air (kOH ∼ 27s−1) to 3.6× 106 cm−3 in relatively clean air (kOH ∼ 5s−1). These values are nearly 2-fold larger than OH concentrations observed in previous winter campaigns in Birmingham, Tokyo, and New York City. During this campaign, the total primary production rate of ROx radicals was dominated by the photolysis of nitrous acid accounting for 46 % of the identified primary production pathways for ROx radicals. Other important radical sources were alkene ozonolysis (28 %) and photolysis of oxygenated organic compounds (24 %). A box model was used to simulate the OH, HO2 and RO2 concentrations based on the observations of their longlived precursors. The model was capable of reproducing the observed diurnal variation of the OH and peroxy radicals during clean days with a factor of 1.5. However, it largely underestimated HO2 and RO2 concentrations by factors up to 5 during pollution episodes. The HO2 and RO2 observed-tomodeled ratios increased with increasing NO concentrations, indicating a deficit in our understanding of the gas-phase chemistry in the high NOx regime. The OH concentrations observed in the presence of large OH reactivities indicate that atmospheric trace gas oxidation by photochemical processes can be highly effective even during wintertime, thereby facilitating the vigorous formation of secondary pollutants.

Design of a rugged 308 nm tunable UV laser for airborne LIF measurements on top of Zeppelin NT

In this work, a detailed analysis and redesign of a tunable UV laser is presented. The laser is part of measurement system of “IEK 8, Forschungszentrum Jülich” for airborne LIF analysis of the OH-radical concentration. The design concept of the laser comprises a frequency doubled Nd:YAG laser as pump source, a dye as active medium to emit light at 616 nm, and a NLO crystal as intracavity frequency doubler. The output wavelength is tunable by a combination of dispersion prisms and an etalon. During measurement campaigns, the laser is mounted on top of Zeppelin NT and therefore is exposed to temperatures ranging from 10 to 40 °C and ambient pressures from 800 to 1000 hPa. In former flights the output power of an existing laser decreased rapidly and the wavelength was unstable during the flights and therefore hinders continuous measurements. The analysis of the existing laser combines a theoretical study of tolerance requirements with experimental testing of opto-mechanical components and of the entire laser system in a climatic test chamber. The performance of the laser is measured over the expected temperature range. It is shown that changing the baseplate temperature by a few Kelvin stops laser emission completely. The optical mounts that are used in the laser and worthwhile alternatives were tested separately in the climatic chamber. The stability of the best mounts exceeds those currently used by a factor of 50. A new laser has been built based on the results of the analysis and further experiments for an optical redesign. This laser was on a field campaign for several weeks and worked reliably.